Derivative of 6-amino-1 2 3 4-tetrahydroquinoline as superadditive in developing composition

ABSTRACT

Photographic developing compositions comprising hydroquinone and a quinoline derivative having the formula   WHEREIN R1 is an alkyl group comprising from one to five carbons atoms, R2 is an alkyl group comprising from one to five carbon atoms, and R3 is hydrogen, or an alkyl group comprising from one to five carbon atoms, at most one of R1, R2 and R3 being substituted alkyl are described. These compositions provide super-additive development in photographic processes.

United States Patent [72] Inventors Jozef Frans Willems Wilrljk; GeorgeFrans Van Veelen, Mortsel, both of Belgium [2i] Appl. No. 727,358

[22] Filed May 7, 1968 [45] Patented Oct. 26, 1971 [73 1 AssigneeGevaert-AGFANV Mortsel, Belgium [32] Priority May 24, 1967 [33] GreatBritain [54] DERIVATIVE OF 6-AMINO- l,2,3,4- TETRAI-IYDROQUINOLINE ASSUPERADDITIVE IN DEVELOPING COMPOSITION 8/1966 Willems et al.

OTHER REFERENCES Willems, et al. (ll): Photographic Science andEngineering, Vol. 10, pages 306- 313(1966) Primary E.raminer-Norman G.Torchin Assistant Examiner- Won H. Louie, Jr. Attorney-Alfred W. BreinerABSTRACT: Photographic developing compositions comprising hydroquinoneand a quinoline derivative having the formula wherein R is an alkylgroup comprising from one to five carbons atoms. R. is an alkyl groupcomprising from one to five carbon atoms, and R is hydrogen, or an alkylgroup comprising from one to five carbon atoms, at most one of R,, R andR being substituted alkyl are described. These compositions providesuper-additive development in photographic processes.

DERIVATIVE OF 6-AMINO- 1 ,2,3,4- TETRAHYDROQUINOLINE AS SUPERADDITIVE INDEVELOPING COMPOSITION The invention relates to a process for thedevelopment of photographic materials, Containing exposed silver halide,and to developing compositions used therein.

It is known that the developing activity of a developing solutioncontains a mixture of several developing substances can be higher thanthe sum of the developing activities of the separate developingsolutions of each of these developing substances used in the sameconcentration as in the solution of that mixture. This phenomenon iscalled the superadditive development.

The most common example of superadditive development is that of thecombination of p-monomethylaminophenol hemisulfate and hydroquinone,which has been described by G. Pizzighelli, Lietfaden der prakrischenPhotographic, Auflage l4(Pau1Nanneke)p. 177.

It is further known from British Pat. specification No. $42,502 that thecombination of hydroquinone and l-phenyl- 3-pyrazolinone has a moreintense developing action than the combination of hydroquinone andpmonomethylaminophenol hemisulfate.

In our British Pat. specification No. 989,383 it has been described thatdeveloping baths with a mixture of hydroquinone and particularp-phenylene diamine derivatives selected fromN,N'-tetraalky1-p-phenylene diamines of which one of the alkyl groupsmay be substituted by water-solubilizing groups such as hydroxyl andsulfo, 6-amino-l,2,3,4- tetrahydroquinoline and6-amino-l-alkyl-tetrahydroquinolines have a higher developing activitythan the combination of hydroquinone and p-monomethylaminophenolhemisulfate and show the advantage over the combination of hydroquinoneand l-phenyl-3-pyrazolidinone of being stable to hydrolysis even instrong alkaline medium.

It has now been found that an exceptional superadditive developingactivity is obtained when using, in the development of exposed silverhalide emulsion layers, a combination of developing agents consisting ofhydroquinone and a com pound corresponding to the general formula:

R1 (IDH on, \C/

wherein R stands for lower alkyl comprising from one to five carbonatoms,

R, stands for lower alkyl comprising from one to five carbon atomsincluding substituted lower alkyl e.g. hydroxyalkyl, carboxyalkyl, thegroup R-NHSO R wherein each of R and R stands for lower alkyl, the groupXSO; M wherein X stands for a straight chain or branched alkyleneradical having from two to five carbon atoms in straight line and Mstands for hydrogen, an alkali metal atom such as sodium or potassium,ammonium or an amine and R stands for hydrogen, lower alkyl comprisingfrom one to live carbon atoms including substituted lower alkyl e.g.alkyl substituted as exemplified for R at most one of R and R beingsubstituted alkyl.

The combinations of developing agents according to the invention show ascompared with the developing combinations described in our British Pat.specification No. 989,383 a markedly higher development activity. Inmost cases they even have a higher activity than the developingcombination of hydroquinone and 1-phenyl-3-pyrazolidinone. Moreover, thedeveloping compositions of the invention have the further advantage ofbeing stable to hydrolysis, even in strong alkaline medium whereascompositions with l-phenyl-3- pyrazolidinone hydrolyse in strongalkaline baths. Thus with the developing combinations of the inventionvery stable developing solutions are obtained which is pahticularlyinteresting for preparing liquid developers.

The compounds corresponding to the above general formula can be added tothe developing bath in the form of free bases as well as in the form oftheir salts e.g. as hydrochloride, as sulfate, etc.

The following are examples of compounds corresponding to the abovegeneral formula:

1. o-diethylaminol ,2,3,4-tetrahydroquinoline dihydrochloride; 2.l-ethyl-6-diethylamino-1,2,3 ,4-tetrahydroquinoline 7. l-(2-methylsulfonylamino-ethyl )-6-diethylaminol,2,3,4-tetrahydroquinolinedihydrochloride; 8. 1-( 3-carboxypropyl)-6-dimethylamini-l ,2,3,4-

tetrahydroquinalone.

The 6-aminc-tetrahydroquinoline derivatives of use according to thepresent invention can be prepared by alkylation of6-amino-tetrahydroquinolines or by alkylation of6-dialkylamino-tetrahydroquinolines. The6-dialkylaminotetrahydroquinolines are prepared by hydrogenation of the6- dialkylaminoquinolines, which in their turn can be prepared asdescribed in Bull. Soc. Chim. Fr. 27 1920) 430.

The following preparations illustrate more particularly how the6amino-tetrahydroquinoline derivatives of use according to the inventioncan be prepared.

Preparation 1:.Compound l A solution of g. (0.4 mole) ofo-diethylamino-quinoline in 400 ml. of anhydrous ethanol ishydrogenated, using 8 ml. of Raney nickel as catalyst, in a sealed tubeat 70 C. and a hydrogen pressure of 1,500 p.s.i. The uptake of hydrogenis complete after min. The catalyst is filtered ofi and the filtrate istreated with 200 ml. of concentrated hydrochloric acid. Afterevaporation of the alcohol the residue is recrystallized from a mixtureof ethanol and ethyl acetate. Melting point: C.

Preparation 2: Compound 2 40.4 g. (0.2 mole) of 6-diethylamino-l,2,3,4-tetrahydroquinoline and 18.2 g. (0.1 mole) of triethylphosphate areheated for 3 hours in an oil bath at 200 C. After having been cooled to50 C. a solution of 15 g. of sodium hydroxide in 50 ml. of water isadded and heating is continued for 90 min. The reaction mixture istreated with water and extracted with ether. After evaporation of theether the residue is distilled. The l-ethyl-6diethylamino-l,2,3,4-tetrahydroquinoline has a boiling point of 184-l87 C./14 mm. It isconverted into its dihydrochloride by treating the base, dissolved inethanol, with alcoholic hydrochloric acid. Melting point: 172 C. (afterrecrystallization from a mixture of ethanol and ethyl acetate).

Preparation 3 Compound 3 80.8 g. (0.4 mole) of 6-diethylamino-l,2,3,4-tetrahydroquinoline and 54.4 g. (0.4 mole) of butane sultone are heatedfor 3% hours, in an oil bath at C. The reaction mixture is dissolved in750 ml. of water and treated with 16 g. (0.4 mole) of sodium hydroxidedissolved in 75 ml. of water. The aqueous layer is extracted three timeswith ether. Then the aqueous layer is treated with 160 ml. of 2.5Nhydrochloric acid and evaporated. The residue is boiled with 500 ml. ofanhydrous ethanol. The undissolved sodium chloride is filtered off andthe ethanol filtrate is evaporated. The product is dried bisulfites,metabisulfites, sultites, and acids such as boric acid and citric acid.The developing bath may further contain potassium bromide,water-softening agents such as polyphosphates or derivatives of ethylenediamine tetraacetic acid, antifogging agents and moistening agents, aswell as other compounds known in the developing technique.

The pH of the baths can vary within wide limits, preferably betweeneight and 1 1, so that a rapid or slow development can be obtained atwill resulting in high-contrast and low-contrast images respectively.

The ratio of hydroquinone to a G-amino-tetrahydroquinoline derivativeused in the present invention, can be chosen in such a way that the bathcomposition is suited for the development of all kinds of materialsincluding materials having silver chloride emulsion layers of lowsensitivity as well as materials having sensitive silver bromoiodideemulsion layers.

The ratio of hydroquinone to the 6-amino-tetrahydroquinoline derivativesused in the present invention can vary within wide limits. The amountsare, however, generally chosen in such a way that the hydroquinonestrongly outweighs the said derivatives. A strong superadditive effectis already obtained with a ratio of 50 mg. of a said derivative used inthis invention to 5 g. of hydroquinone per liter. Generally the amountof hydroquinone is comprised between 1 and 30 g. per litre and theamount of 6-amino-tethydroquinoline derivative between 5 mg. and 2 g.per liter.

Combinations of developing agents used in this invention may also beapplied in the treating solution and/or in the lightsensitive materialand/or in the image-receiving material used in the application of thesilver complex diffusion transfer process, the principle of which isdescribed in British Pat. specification Nos. 614,155 and 654,630 and inGerman Pat. specification No. 887,733. For more details concerning thesilver complex diffusion transfer process, the different embodiments ofthe materials and apparatus used therein, there can be referred toProgress in Photography 1955-1958, p. 24-36 and the patent literaturecited therein.

The following examples illustrate the present invention.

Example 1 Strips of a photographic material comprising a light'sensitivesilver bromoiodide emulsion layer, coated on material comprisingtriacetate support, are exposed through a grey filter withlight-quantity (E) which corresponds to the shoulder part ofthedensity/log E curve.

One of these film strips is developed in a bath A having the followingcomposition:

sodium carbonate sodium hexametaphosphate 1.0 g. sodium sulfite "0.0 g.potassium bromide 0.5 g. hydroquinone 4.4 8. water up to 1.000 ml.

The other strips are developed in baths having the same composition asbath A but moreover containing an equivalent amount of a developingagent as listed in table 1 given hereinafter.

The results of these developing tests are listed in table 1. Thedensities are determined after a development time of 30, 6060 and 90sec.

propyl-p-phenylene diamine From these results it clearly appears thatthe developing combination of the invention has a higher activity thanthe developing combinations of our British Pat. specification No.989,383.

Example 2 5 ing the following composition:

boric acid 5.0 g. borax I0.0 g. sodium hexametaphosphate 1.0 g. sodiumsulfite 20.0 g. potassium bromide 0.5 g. hydroquinone 4.4 g.

water LIP [O The other strips are developed in developing baths havingthe same composition as bath B, but containing moreover an equivalentamount of a developing agent as listed in table 2 given hereinafter.

The densities are determined after 1, 3 and 5 respectively Table 2Developing bath Density after a developing time of l min. 3 min. 5 minbath 8 0.04 0.04 0.04 bath B+ mg. of compound 1 0.20 1.20 1.60 bath B+mg. of compound 2 0.80 1.45 1.70 bath B+l05 mg. of compound 3 0.05 0.841.25 bath B+70 mg. of l-methyl-oamino-l,Z.3,4-tetruhydroquinolineoxalate 0.05 0.46 1.00 bath B+l07 mg. of N.N-diethyl-N-propyl-N-3-sulphopropyl-p-phenylene diamine 0.05 0.17 0.58 bath B+50 mg.of l-phenyl-3- pyrazolidinone 0.05 0.46 1.10

From these results it appears that the developing activity of thecombination of developing agents according to the invention is not onlyhigher than that of the developing combinations of our British Pat.specification No. 989,383 but even higher than that of the combinationof 1-phenyl-3- pyrazolidinone and hydroquinone.

Example 3 Strips of a photographic material comprising a silverbromoiodide emulsion layer were exposed through a step wedge anddeveloped for 2 minutes in a developing bath C having the followingcomposition:

sodium carbonate 20.0 g. sodium sulfite 20.0 g. potassium bromide 10 g.hydroquinone 4.5 g. water up to 1.000 ml.

Other strips were developed in baths having the same composition as bathC but moreover containing an equivalent amount of a developing agent aslisted in table 3, hereinafter. These baths were used either directlyafter their preparation or after having been stored for some time inclosed containers at 80 c. The results of the developing tests beforeand after storage are listed in table 3.

From these results it appears, that compound 3 is much more stableagainst hydrolysis than l-phenyl-3-pyrazolidiuone and for this reason isinteresting for preparing liquid developers.

What we claim is:

I l. Photographic developing composition comprising hydroquinone and aderivative of 6-amino-l,2,3,4- tetrahydroquinoline corresponding to thefollowing general formula, in the form of the free base or in its saltform 3 R1 ?H2 \N CH: 0 R2 Hz wherein R is an alkyl group comprising fromone to five carbon atoms.

R is an alkyl group comprising from one to five carbon atoms, and

R is hydrogen, or an alkyl group comprising from one to five carbonatoms,

at most one of R R and R being substituted alkyl.

2. Photographic developing composition according to claim 1, wherein oneof R,, R and R is a hydroxyalkyl group, a carboxyalkyl group, or thegroup R-NHSO R wherein each of R and R is a lower alkyl group, the group-X-SO M wherein X is a straight or branched alkylene group having fromtwo to five carbon atoms in straight line, and M is hydrogen, an alkalimetal, ammonium or an amine.

3. Photographic developing composition according to claim 1, whereineach of R and R is a lower alkyl group having from one to five carbonatoms, and R is hydrogen, a lower alkyl group having from one to fivecarbon atoms or the group -X-SO M wherein X is a straight or branchedalkylene group having from two to five carbon atoms in straight line,and M is hydrogen, an alkali metal, ammonium or an amine.

4. Photographic-developing composition according to any of claim 1,wherein the said hydroquinone is present in an amount of from 1 to 30 g.per litre and the said 6-aminol,2,3,4-tetrahydroquinoline derivative inan amount offrom 5 mg. to 2 g. per litre.

5. Photographic-developing method comprising developing and exposedsilver halide emulsion layer of a photographic material an means ofhydroquinone and a 6- aminol,2,3,4tetrahydroquinoline derivative asdefined in claim 1.

6. Photographic-developing method according to claim 5, for applicationin the silver complex diffusion transfer process wherein the exposedlight-sensitive material is developed with an aqueous alkaline solutionin the presence of hydroquinone and ao-amino-l,2,3,4-tetrahydroquinoline derivative as defined in claim 1.

UNITED STATES PATENT OFFICE i ifIERTIFICATE OF CORRECTION Patent No 3,615, 52 5 Dated October 26, 1817] imentorfs) JOZEF FRANS WILLEMS ET ALIt is certified that error appears in the above-identified patent andthat said Letters Patent are hereby corrected as shown below:

Title page under References Cited, United States Patents, 727, 358"should read 3, 265, 502 Column 1, line 9, "contains" should readcontaining Column 2, line 17 (NO. 5), (N-ethyl-nN-3--suli'o1oropylgamino)" should read (N-ethyl-N-S-sulphopropyl-amino)- 7 Column 2, lines24 25 (No. 8), "6dimethylamini-1, 2, 3,4-tetrahydrot tinalone" shouldread 6-dimethylamino- 1, 2, 3, 4-tetrahydroouinoline Column 3, line 16,after "having insert highly Column 3, lines 43 44, "material comprising"should read a ceiulose Column 3, line 45, after "with" insert a Column3, line 61, "6060" should read 6O Column 4, line 28, after "5" insermin. Column 6, lines 20 21, claim 4, after "according to dei te any ofColumn 6, line 26, claim 5, "and" should read an Column 6, line 27,claim 5, "an" should read by Column 6, line 28, amino 1, 2, 3,4tetrahydroquinoline" should read amino- 1, 2, 3, 4-tetrahydroquinolineSigned and sealed this 16th day of December 1973.

(SEAL) Attest:

EDlJARD M. FLETCHER, JR. RENE D. TEGTliEZ'ER Attesting; Officer ActingCommissioner of Patents RM F'O-WULO r10-69) USCOMM oc 6037B P59 U 5GOVERNMENT PRINTING OFFICE 1969 D-36i33l,

2. Photographic developing composition according to claim 1, wherein oneof R1, R2 and R3 is a hydroxyalkyl group, a carboxyalkyl group, or thegroup -R-NHSO2R4 wherein each of R and R4 is a lower alkyl group, thegroup -X-SO3M wherein X is a straight or branched alkylene group havingfrom two to five carbon atoms in straight line, and M is hydrogen, analkali metal, ammonium or an amine.
 3. Photographic developingcomposition according to claim 1, wherein each of R1 and R2 is a loweralkyl group having from one to five carbon atoms, and R3 is hydrogen, alower alkyl group having from one to five carbon atoms or the group-X-SO3M wherein X is a straight or branched alkylene group having fromtwo to five carbon atoms in straight line, and M is hydrogen, an alkalimetal, ammonium or an amine.
 4. Photographic-developing compositionaccording to any of claim 1, wherein the said hydroquinone is present inan amount of from 1 to 30 g. per litre and the said6-amino-1,2,3,4-tetrahydroquinoline derivative in an amount of from 5mg. to 2 g. per litre.
 5. Photographic-developing method comprisingdeveloping and exposed silver halide emulsion layer of a photographicmaterial by means of hydroquinone and a6-amino-1,2,3,4-tetrahydroquinoline derivative as defined in claim
 1. 6.Photographic-developing method according to claim 5, for application inthe silver complex diffusion transfer process wherein the exposedlight-sensitive material is developed with an aqueous alkaline solutionin the presence of hydroqUinone and a6-amino-1,2,3,4-tetrahydroquinoline derivative as defined in claim 1.